# Bis(trimethylsilyl)phosphide chemistry: a half-century of advances across the periodic table

## TL;DR

This review explores the chemistry of bis(trimethylsilyl)phosphide ligands over 55 years, highlighting their unique structures and potential in catalysis and materials science.

## Contribution

The paper provides a comprehensive review of the synthesis, structure, and reactivity of bis(trimethylsilyl)phosphide complexes across the periodic table.

## Key findings

- Bis(trimethylsilyl)phosphide complexes show diverse coordination modes and reactivity profiles.
- These ligands offer unique structural motifs compared to bis(trimethylsilyl)amide ligands.
- They have potential applications in catalysis, materials science, and bioinorganic chemistry.

## Abstract

Whilst bis(trimethylsilyl)amide has been used extensively as a ligand across the periodic table, the chemistry of its heavier group 15 congeners is relatively underdeveloped. However, bis(trimethylsilyl)phosphide coordination chemistry has provided unique structural motifs and has also shown potential applications in catalysis, materials science, and bioinorganic chemistry. This review, which marks 55 years since the first report of a bis(trimethylsilyl)phosphide complex, provides a comprehensive overview of the synthesis, characterisation and reactivity of structurally authenticated s-, p-, d- and f-block metal complexes of this ligand, focusing on salient single crystal XRD and NMR spectroscopic data. We discuss the factors influencing the diverse coordination modes and reactivity profiles of bis(trimethylsilyl)phosphide complexes, together with an overview of their potential as precursors for novel solid-state materials, aiming to inspire future research endeavours using this ligand. We also review the small number of bis(triisopropylsilyl)phosphide complexes, in order to provide motivation for the future study of other bis(silyl)phosphide ligands.

We review structurally authenticated metal(loid) bis(trimethylsilyl)phosphide complexes, highlighting how their solid-state structures and electronic structures differ from those containing the related bis(trimethylsilyl)amide ligand.